Role of submerged vegetation in the retention processes of three plant protection products in flow-through stream mesocosms.

Quantitative information on the processes leading to the retention of plant protection products (PPPs) in surface waters is not available, particularly for flow-through systems. The influence of aquatic vegetation on the hydraulic- and sorption-mediated mitigation processes of three PPPs (triflumuron, pencycuron, and penflufen; logKOW 3.3-4.9) in 45-m slow-flowing stream mesocosms was investigated. Peak reductions were 35-38% in an unvegetated stream mesocosm, 60-62% in a sparsely vegetated stream mesocosm (13% coverage with Elodea nuttallii), and in a similar range of 57-69% in a densely vegetated stream mesocosm (100% coverage). Between 89% and 93% of the measured total peak reductions in the sparsely vegetated stream can be explained by an increase of vegetation-induced dispersion (estimated with the one-dimensional solute transport model OTIS), while 7-11% of the peak reduction can be attributed to sorption processes. However, dispersion contributed only 59-71% of the peak reductions in the densely vegetated stream mesocosm, where 29% to 41% of the total peak reductions can be attributed to sorption processes. In the densely vegetated stream, 8-27% of the applied PPPs, depending on the logKOW values of the compounds, were temporarily retained by macrophytes. Increasing PPP recoveries in the aqueous phase were accompanied by a decrease of PPP concentrations in macrophytes indicating kinetic desorption over time. This is the first study to provide quantitative data on how the interaction of dispersion and sorption, driven by aquatic macrophytes, influences the mitigation of PPP concentrations in flowing vegetated stream systems.

Simultaneous analysis of free and sulfo-conjugated steroid estrogens in artificial urine solution and agricultural soils by high-performance liquid chromatography.

A simple and robust analytical method was developed to simultaneously detect and quantify 17ß-estradiol (E2), estrone (E1), 17ß-estradiol-3-sulphate (E2-3S), and estrone-3-sulphate (E1-3S) in aqueous solutions (calcium chloride and artificial urine solutions) and agricultural soils using high performance liquid chromatography and UV detection. The standards for all four compounds were linear in the range of 0.01 to 1.0 µg mL(-1) (n = 6) and 1.0 to 20 µg mL(-1) (n = 6), respectively, with correlation coefficients > 0.999. The on-column limits of detection at an injection volume of 50 µL and S/N (signal: noise) ratio of 3 were: 9.0 ng mL(-1), 10 ng mL(-1), 5.0 ng mL(-1), and 7.0 ng mL(-1) for E2-3S, E1-3S, E2 and E1, respectively. The limit of detection and quantification in artificial urine solution and CaCl(2) solution was 1.0 ng mL(-1) for all four compounds. Method detection limits for the compounds in the 3 soils ranged from 2 to 2.4 ng g(-1) (E2-3S and E1-3S), and 1.0 to 2.9 ng g(-1) (E2 and E1), respectively.

Sorption of estrone and estrone-3-sulfate from CaCl2 solution and artificial urine in pastoral soils of New Zealand.

Estrone (E1) and its sulfate conjugate estrone-3-sulfate (E1-3S) are released to the environment in animal wastes in significant amounts, and direct exposure occurs in grazed pasture systems. Both compounds have been shown to potentially contribute to endocrine disruption in wildlife, and knowledge about the sorption behavior of these compounds is necessary for a sound risk assessment. For labile compounds such as E1 and E1-3S, however, the standard protocols might overestimate sorption by not considering metabolite formation or allowing for equilibration that exceeds the commonly reported half-lives of these compounds. We therefore conducted modified batch sorption experiments with 0.005 M calcium chloride (CaCl2) and artificial urine solution to determine the influence of the mediator solution on the sorption of E1 and E1-3S in three pasture soils from New Zealand. Sorption isotherms of both compounds were nonlinear, and the Freundlich equation was found adequate to describe the isotherms. The sorption potential of E1-3S was about one order of magnitude lower than for the free counterpart, and the Kf values significantly changed between the two mediator solutions. The calculation of concentration-dependent effective distribution coefficients (Kdeff) revealed that for a range of realistic exposure concentrations in a grazed dairy system, the common approach of using CaCl2 would deliver incorrect inferences for a sound risk assessment.

Degradation and metabolite formation of 17beta-estradiol-3-sulphate in New Zealand pasture soils.

Estrogens-sulphates such as 17beta-estradiol-3-sulphate and estrone-3-sulphate are excreted by livestock in the urine. These conjugates are precursors to the free counterparts 17beta-estradiol and estrone, which are endocrine disrupting chemicals. In this study microcosm laboratory experiments were conducted in three pasture soils from New Zealand to study the aerobic degradation and metabolite formation kinetics of 17beta-estradiol-3-sulphate at three different incubation temperatures. The degradation of 17beta-estradiol-3-sulphate followed a first-order kinetic and the temperature dependence of the rate constants was sufficiently described by the Arrhenius equation. Degradation was different between the three investigated soils and the rate constants across the soils were significantly correlated to the arylsulphatase activity at 7.5 and 15 degrees C. Estrone-3-sulphate and 17beta-estradiol were identified as primary metabolites and estrone as a secondary metabolite. Results suggest arylsulphatase activity originating from soil microbial biomass is the main driver for the degradation of 17beta-estradiol-3-sulphate.

Modeling degradation and metabolite formation kinetics of estrone-3-sulfate in agricultural soils.

Estrone-3-sulfate (E1-3S), formed in the kidneys of pregnant cattle, can act as a precursor to the free hormone estrone (E1) known for its endocrine disrupting potential in wildlife. Laboratory microcosm studies were conducted to investigate the aerobic degradation of E1-3S in three contrasting pasture soils at 7.5, 15, and 25 degrees C. Deconjugation of E1-3S resulted in the formation of the metabolite E1. Two kinetic models-a single first-order and a biexponential kinetic model-were applied to fit the observed degradation dynamics and to derive degradation end-points (DT50 and DT90) for the parent compound and the metabolite for each condition. Model selection and evaluation of their performance were based on a suit of statistical measures (one-way ANOVA, AIC(c), R2(adj), chi2 error-%, and SRMSE). The results showed rapid initial degradation of E1-3S, followed by a much slower decline with time, and rate of degradation was temperature dependent. The DT50 and DT90 values of E1-3S ranged from a few hours to several days, while the formation of the major metabolite (E1) was concomitant with E1-3S degradation in all nonsterile soils. The parent compound degradation and formation and subsequent dissipation of metabolite were successfully predicted by both models, however, the nonlinear biexponential model improved the goodness-of-fit parameters in most cases.

Retention of estrogenic steroid hormones by selected New Zealand soils.

We performed batch sorption experiments for 17beta-estradiol (E2) and 17alpha-ethynylestradiol (EE2) on selected soils collected from dairy farming regions of New Zealand. Isotherms were constructed by measuring the liquid phase concentration and extracting the solid phase with dichloromethane, followed by an exchange step, and analysis by HPLC and UV detection. The corresponding metabolite estrone, (E1) formed during equilibration of E2 with soil was taken into account to estimate the total percentage recoveries for the compounds, which ranged from 47-105% (E2 and E1) and 83-102% (EE2). Measured isotherms were linear, although some deviation from linearity was observed in a few soils, which was attributed to the finer textured particles and/or the allophanic nature of the soils having high surface area. There was a marked difference in K(d)(eff) (effective distribution coefficient) values for E2 and EE2 among the soils, consistent with the soils organic carbon content and ranged from 14-170 L kg(-1) (E2), and 12-40 L kg(-1) (EE2) in the soils common for both compounds. The sorption affinity of hormones in the soils followed an order: EE2